Metallised pigments

ABSTRACT

An unsymmetrical compound having either the formula:   WHEREIN M is a transition metal atom, X and Y are the same or different, and each is hydrogen or each represents a non water solubilising group, and Z has the same significance as X and Y, or two adjacent X groups or two adjacent Y groups or two adjacent Z groups form a fused arylene, and k, m and n are the same or different and each is an integer from 1 to 4; or the formula:   WHEREIN M, X, Y, m and k have their previous significance, R1 and R11 are the same or different and each is an alkyl residue having from 1 to 4 carbon atoms or an aryl residue and R111 is hydrogen or an arylazo residue.

United States Patent [191 Inman et al.

1 1 METALLISED PIGMENTS [75] Inventors: Eric Richard Inman, Bridge ofWeir; James McGeachie McCrae, Stewarton; John Andrew Stirling, Glasgow,all of Scotland [73] Assignee: Ciba-Geigy Corporation, Ardsley,

[22 Filed: Mar. 15, 1973 21 Appl. No.: 341,415

[30] Foreign Application Priority Data Mar. 20, 1972 United Kingdom12822/72 [52] U.S. Cl. 260/429.9; 106/288 Q; 260/4381; 260/439 R;260/566 F [51] Int. Cl. C07f 3/06; C07f 13/00; C07f 15/04 [58] Field ofSearch 260/4299, 438.1, 439 R, 260/566 F, 288 Q, 439 R [56] ReferencesCited UNITED STATES PATENTS 2,847,472 8/1958 Robertson 260/566 F2,993,065 7/1961 Kumins et al. 260/439 R 3,303,162 2/1967 Fuchsman260/439 R 3,388,141 6/1968 Berenbaum 260/439 C 3,440,254 4/1969 Lenoiret a1. 260/429 R 3,457,301 7/1969 Lenoir et al. 106/288 Q 3,472,87610/1969 Klein 260/439 R 3,687,991 8/1972 Gaeng 260/4299 3,700,70910/1972 Inman 6t a1 106/288 Q 3,723,490 3/1973 Inman et al 106/288 QFOREIGN PATENTS OR APPLICATIONS 1,075,582 7/1967 United Kingdom1,297,561 5/1962 France Primary ExaminerPatrick P. Garvin AssistantExaminer-A. P. Demers Attorney, Agent, or FirmVincent J. Cavalieri [57]ABSTRACT An unsymmetrical compound having either the formula:

[ 1 July 15, 1975 Q/WK m C M W wherein M is a transition metal atom, Xand Y are the same or different, and each is hydrogen or each representsa non water solubilising group, and Z has the same significance as X andY, or two adjacent X groups or two adjacent Y groups or two adjacent Zgroups form a fused arylene, and k, m and n are the same or differentand each is an integer from 1 to 4; or the formula:

wherein M, X, Y, m and k have their previous significance, R and R arethe same or different and each is an alkyl residue having from 1 to 4carbon atoms or an aryl residue and R is hydrogen or an arylazo residue.

13 Claims, No Drawings METALLISED PIGMENTS The present invention isconcerned with a new class of metallised bisazomethine compounds ofvalue as pigment, and with novel azomethines and bisazomethines of usein the production of these compounds.

The invention provides novel unsymmetrical compounds of formula:

wherein M is a transition metal atom, X and Y are the same or differentand each is hydrogen or a non-water solubilising group and Z has thesame significance as X and Y, two adjacent X groups or two adjacent Ygroups or two adjacent Z groups may form a fused arylene ring, which mayitself carry further non-water solubilising substituents, and K, m and nare the same or different and each is an integer from 1 to 4; or

wherein M, X, Y, m and K have their previous significance, R and R arethe same or different and each is an alkyl residue having from 1 to 4carbon atoms or an aryl residue and R is hydrogen or an arylazo residue.

With regard to the unsymmetrical compounds of formula I, it will beappreciated that when Y and Z are the same and n are the same, then thepositions of Y and Z in their respective benzene nuclei are differentrelative to the respective oxygen atoms attached to these nuclei.

Examples of transition metal atoms which may be present in compounds Iand II are members of the first group of transition elements of thePeriodic System of Elements such as zinc and especially copper ornickel. Examples of non-water solubilising substituents X, Y and Zinclude halogen, alkyl and alkoxy groups having from 1 to 4 carbon atomsin the alkyl moiety, nitro and carboxy groups arylazo groups and fusedarylene residues.

Although carboxy groupsare usually considered to be groups which impartwater-solubility to a pigment or dyestuff molecule, in the case ofcompounds of formula I and I] wherein the carboxy group is ortho to theoxygen atom in the naphthylene residue, the carboxy group does notimpart any appreciable water-solubility or alkali-sensitivity to thecompound of formula I or II.

Examples of aryl substitutents R, and R are substituted or unsubstitutedphenyl and aor B-naphthyl residues.

Examples of arylazo residues R are phenylazo and aand ,B-naphthylazoresidues optionally substituted by one or more non water-solubilisinggroups, examples of which are as hereinbefore described.

A preferred sub-group of compounds of the formula l are those having theformula:

wherein X Y and Z are the same or different and each is a non-watersolubilising group.

Preferred instances of group X are an alkyl group having from 1 to 4carbon atoms, a nitro group, a halo gen atom or a phenoxy group;preferably Y is hydrogen or a carboxy group; and preferably Z ishydrogen.

wherein X, Y, Z, K, m and n have their previous significance, with ano-hydroxy aldehyde having the formula:

wherein Y, Z, In and n have their previous significance, to produce acompound having the formula:

wherein X, Y, Z, K, m and n have their previous significance, and thenmetallising the reaction product V.

The condensation step of the reaction of compounds III and IV may beeffected in solution or in a finely dispersed suspension with goodagitation using either water or an organic solvent as the reactionmedium. The reaction is conveniently effected at an elevatedtemperature, usually between 50C and the reflux temperature dependingupon the reactants and the solvent used. Preferably, the progress of thereaction is monitored to ensure that the reaction is proceeding at asatisfactory rate and that the end product is not being rendered impureby side reactions such as disproportionation.

Metallisation of the reaction product V may be carried out in situ, orthe reaction product may be filtered off, washed and re-suspended in thesame or a different solvent prior to metallisation. Metallisation may beeffected using a solution of any soluble transition metal salt. Forcoppering, an aqueous solution of copper acetate, cuprammonium sulphateor sodium cuprotartrate can be used. In the case of metallisation withzinc. an alcoholic solution of zinc acetate can be used. Whenmetallisation is effected using nickel, it is convenient to use asolution of nickel acetate tetrahydrate in dimethyl formamide.

The compounds of formula III are new and form part of this invention.These compounds may be produced by reacting together the correspondingo-hydroxy aldehyde and o-arylene diamine in solution or as afinelydispersed suspension, with efficient agitation, in either water oran organic solvent at a reaction temperature below 60C, preferably atambient temperature. for sufficient time to enable the reaction to go tocompletion. The time for completion of the reaction varies from 30minutes to 4 hours depending upon the nature of the reactants and theconditions employed. It is particularly convenient to carry out thereaction in an aqueous suspension or solution in the presence of a mildreducing agent such as sodium bisulphite for instance in the ratio of 2mols of bisulphite to 1 mol of aldehyde. In this way the reaction isfacilitated and contamination of the product with oxidation products,which would have a deleterious effect on the brightness and otherphysical properties of the product is avoided. Small amounts that isless than 1% by weight of the calculated weight of the product of asurfactant may be added with advantage-when working in an aqueousmedium.

Although a variety of organic solvents for instance alcohols, ketones,esters or hydrocarbons may be employed instead of water as the reactionmedium, this is less preferred because disproportionation to a mixtureof bisazomethine and free o-arylene diamine can occur in organicsolvents.

Disproportionation may also occur on heating a solution or suspension ofa compound of formula III, or on drying or storing it. For this reasonit is particularly advantageous to react them with compounds of formulaIV without any further treatment other than filtration and washing.

The compounds of formula V are also new and these compounds also formpart of this invention.

According to a further aspect of the present invention there is provideda process in which a compound of formula III as hereinbefore defined isreacted with, respectively, a metal salt of an o-hydroxy aldehyde offormula IV, the salt having the formula:

--CH=O or (Z) wherein R,, R R and M have their previous significance toproduce a compound of formula II.

The compounds of formula I and 11 may be employed as pigments directlyafter their production according to the process of the invention. thatis after they have been filtered off from their reaction mixtures anddried. Alternatively, they may first be further processed using knownwet or dry conditioning techniques such as grinding, either alone or inthe presence of a watersoluble salt or other medium which can besubsequently be removed, for instance by washing.

Because of their economical and easy mode of production combined withtheir excellent pigmentary properties, the compounds of formula I and IIare valuable as pigments in a wide variety of organic media, for examplesurface coatings, inks and polymers.

The compounds of formula I and II are valuable pigments which in afinely divided form can be used for pigmenting high molecular organicmaterial, for example cellulose ethers and cellulose esters, such asethylcellulose, cellulose acetate, cellulose butyrate, polyamides orpolyurethanes or polyesters, natural resins or synthetic resins, such aspolymerisation resins, for example aminoplasts, especiallyurea-formaldehyde and melamine-formaldehyde resins, alkyd resins,phenoplasts, polycarbonates, polyolefines, such as polystyrene,polyvinyl chloride, polyethylene polypropylene, polyacrylonitrile,polyacrylic acid esters, rubber, casein, silicone and silicone resins,individually or as mixtures.

At the same time it is immaterial whether the high molecular weightcompounds mentioned are in the form of plastic masses, melts or spinningsolutions, lacquers, paints or printing inks.

Depending on the end use, it is advantageous to use the new pigments aspure pigment powder or in the form of a dispersion of a pigment in aresin. Resins suitable for use as carriers in pigment dispersionsinclude natural resins, for example abietic acid or its esters,ethylcellulose, cellulose acetobutyrate, alkaline earth salts of higherfatty acids, fatty amines, for example stearylamine or rosinamine, vinylchloride-vinyl acetate copolymers, polyacrylonitrile or polyterpeneresins or water-soluble dyestuffs, for example dyestuffsulphonic acidsor their alkaline earth metal salts.

Some Examples will now be given; parts and percentages are expressed byweight unless otherewise stated. Examples 1 to 11 illustrate theproduction of compounds of formula III; Examples 12 to 20 illustrate theproduction of compounds of formula V or VII; and Examples 21 to 74illustrate the production of compounds of formulae I and II.

EXAMPLE 1 10.8 Parts of o-phenylene diamine were stirred in 500 parts ofwater containing 0.1 parts of a commercial nonionic surfactant usinghigh speed shear agitation at 20C. 12.2 Parts of salicylaldehyde wereadded over three hours and the temperature rose to 45C. Stirring wascontinued for a further 2 hours and the resultant bright yellowsuspension was filtered and the filter-cake was washed with 1,000 partsof water and then air dried. In this way, there were obtained 16.5 parts(78%) of a yellow powder m.p. 656C having the formula:

NR2 no EXAMPLE 2 tant orange-brown suspension was stirred for 1 hour,-

then filtered and the filter-cake washed with 1,500 parts of water anddried.

There were obtained in this 16.0 parts of an orangebrown solid mp.ll920C which was free of byproducts when examined by thin layerchromatography.

EXAMPLE 3 4.3 Parts of 2-hydroxy-l-naphthaldehyde, 3.83 parts of3,4-diamino-nitrobenzene were suspended in a mixture of 7.5 parts water,30 parts acetone and 0.1 parts a commerical nonionic surfactant and themixture was stirred for 15 minutes. A solution of 1.0 part of sodiumhydroxide in 12.5 parts of water was added and the suspension wasstirred for a further 15 minutes. 7.6 Parts of sodium bisulphite wereadded and stirring continued for a further 2 hours. The resultantred-brown suspension was filtered, the filtercake washed with 1,000parts of water and dried giving 7.0 parts ofa brown-red powder.

EXAMPLE 4 10,000 parts of water, until the washes were free of sulphate,giving a paste containing parts (88%) of a bright yellow solid. A sampleof this paste was dried and found to have a melting-point of -1C.

EXAMPLE 5 17.2 Parts of 2-hydroxy-1-naphthaldehyde and 10.8 parts ofo-phenylene diamine were stirred together at room temperature in 500parts of ethanol for 3 hours. The resultant orange precipitate wasfiltered off and the filter-cake washed with 500 parts of ethanol anddried, yielding 24.0 parts (92.0%) of an orange-yellow solid of m.p.162-4C which was identical with the product of Example 4.

7 EXAMPLE 6 8.6 Parts of Z-hydroxy-l-naphthaldehyde, 5.4 parts ofo-phenylene diamine and 60 parts of dioxan were stirred in 15 parts ofwater which contained 0.1 parts of a commerical nonionic surfactant forminutes. A solution of 2.0 parts of sodium hydroxide dissolved in partsof water was added and after 15 minutes stirring, 7.6 parts of sodiumbisulphite was added and stir- Table l Ex. Diamine ohydroxy- ProductYield m.p.

aldehyde NH 3 7 Q c Ho NQ 90 l-90 OH OH NH 2 s Q c Ho 96 225-55 H3C NH2NH2 OH CO H OH co n cHo N 9 "H2 225-35 NH 2 OH OH NH l0 m cHo as 118-20N c NH l NH2 2 on OH OH NH E s CHO 9 10 EXAMPLE l2 ethanol and dried,producing 27.5 parts.of an orange solid mp. 269-70C. I 24.0 Parts of themonoazomethine product of Exam- By substituting an equivalent amount ofthe appropriple 4 and 23.6 parts ofvl-formyl-2-hydroxy-3-naphthoic atemonoazomethine and o-hydroxy aldehyde or B-diacid were stirred andheated to reflux in 500 parts of 5 ketone, the products in the followingTable ll were obethanol for 2 hours. The resultant orange suspensiontained. Table II also gives the appropriate colour, yield was filtered,the filter-cake washed with 500 parts of and melting point of thevarious products.

Table ll Ex. Azomethine o-hydroxyaldehyde Product Colour 7: mp.

or fl-diketone Yield "G g OH Q 13 :N NH =N N: Yellow 60 204-5 CHO OH o

OH Q 14 I Br CH I :u N Yellow 55 205-6 15 I I m Q Yellow 87 184-6 16 cncocn- Q 3 Yellow 50 220-1 ,cocn

OH HO C H CH G 3 Q 3 OH l7 N I; N Orange 62 170-4 OH HO 5 Br N N- l8 Q nYellow 56 [90-4 CHO OH Ho Table 'II Continued Ex. Azomethineohydroxyaldeh vde Product Colour m.'p.-

or ,B-diketone Yield C 0.. Q V I9 -N N- Orange 79 225-8 N NH K] OH 2 CHOOH HO z co 2H /N N B Red 50 257-60 CHO OH HO EXAMPLE 21 heating then 5.0parts of acetyl acetone in 20 parts of e 1d a lime coloured suspen- 9.2Parts of the roduct of Exam le 12 were stirred alcohol w addgd to yle in250 parts of zrnethoxy ethanolpthen to this were sion. This suspensionwas added to 6.55 parts of the added 1.96 parts of nickel acetatetetrahydrate disfi i f lfi 4.suspende,d z panst of solved in 50 parts ofdimethyl formamide and the mix- 0 f e t h srlllspenstlon was snare hr:rodom emperanture was refluxed for 3 hours. The resultant bright red g?g a L f 2% i g precipitate was filtered, the filter-cake washed with 100K s ta {B i s is: 1,2 parts of Z-methoxy ethanol followed by 500 partsof p l b I ethanol and then dried, giving 8.1 parts (78%) of a 53 ofwhch e deep red solid which did not melt below 360 C. The followingTable III gives compounds prepared in a similar manner to that ofExample 21. Table III also EXAMPLE 22 I gives the appropriate ligand,colour in lacquer, yield 6.25 Parts of nickel acetate tetrahydrate weresusand a summary of the fastness properties of the various pended in 100parts of alcohol and heated to C with 40 pigments produced.

Table III c 1 Ex. Ligand Product il? Fastness Lacquer Yield toLight 23 KRed 89 Excellent OH HO 0 o 24 Golden 82 Excellent Brown 25 J; i YellowGood Table III Continued Colour Ex Ligand Product in 7a Fastness LacquerYield to Light 26 Q Q Red 86 Excellent N Nw/Br N N B OH HO 27 n Y N 51Golden 70 Excellent U C Brown Red 80 Excellent 3 CL 29 N8 N Red 75Excellent OH Ho CO Q C I. 30 ,1 N N Ofgnge 75 Excellent 31 %:=N ufiYellow 70 Good Z i o, \o

32 Q Br N Br Red I00 Excellent i c OH 0 Cl. 3 3 %N EN w Br Brown 92Excellent 0 I Cu O Q 3 I: B

%:N\ Nw/ Yellow 70 Good Table III Continued Colour Ex. Ligand Product inFastness Lacquer Yield to Light Q a 35 N N Orange- 85' Excellent 73 mbrown OH o 0 o ECL 36 %f p Yellow 90 Good o Zn o Q Q 37 N N :w 5i: N -nRed 92 Excellent Ni O OH Ho 0 CH 7 38 Q Orange- 91 Excellent w brown oCu O Q 39 N )R/o Yellow 72 Good 5 40 =jA QI-K J n Red 93 Excellent I OHHO O 0 Cl. Q CL N N Br Q 4| w N N r Red 90 Excellent CO H o CO H Cl Q CL42 Ni N Q Golden 91 Excellent n N N Br brown OH c *0 9 H HO I O/ U \O 2co l-l CL 43 n N 5 /O Yellow 90 Good 0 Zn o COZH Q W; CH 44 N fi N N\/(9 Red 85 Excellent OH o 2 Ho co ll Table III-Continued ('oluur LigandProduct in A Fustnuw Lz cquer Yield [0 Light ECH Yellow 90 Excellent N Ng C fi U l o O CO2H CH3 Q Yellow 80 Good o Zn I I COZH CH3 /CH3 Q Q N BrOrange- 93 Excellent N N'wflr w red O Ho c0 11 0 CO H cH Q N Br Yellow94 Excellent H l w brown u 0 CO2 H Yellow 80 Good 9 N N a N N o OH o C0H cow 0 N02 2 Q a Red 94 Excellent o 7 O Ho 2" co H Q Brown 70 ExcellentU 0 o co n N0 7 v Q Red so Good I N z N :8

O COQH N0 N02 Q 3 OCH Brdwn 93 Excellent N'-\,," ,N- NN-@ Ni OH Ho I 2 o\0 N0 Table -III Continued Colour Ex. Llgand Product in Z FuslncssLacquer Yield luLight 54 2 Brown 90 Excellent Q NN u NO 0 Q 2 CO H 55M02 Golden 86 Good ocH M OCH yellow we "ir fi I! H Ho N0 2 CO2H CH1 CH15 Q Q Red 98 Excellent -N =N Qf N 8 HQ 0 O (0 H CO H OH: 57 Q Golden 96Excellent yellow o CO H 58 Yellow 82 Good ln s CO2H CH3 3 3 3 4 59 g QBrown 92 Excellent N M: O %=N\N/M= 0H 0 Ho co H o co n u co H Q Brown 9|Excellent Red 80 Excellent Table III Continued Colour Ex. Ligand Productin Z Faslness Lacquer Yield to Light 62 Golden 75 Excellent 3 brown N \C/2 U 0 I o CO2H 63 Q Yellow 74 Good 0 Zn o CH3 CO2H CH CH 64 Q 3 g 1 3Golden 70 Excellent N N N brown o 0 OH HO CH 3 CH Q 65 N l N Yellow 75Good cl CH3 c N as N N Red 85 Excellent o 0 OH CH HO" CH 3 Q cll Q 3 67Kg N N Bl N N Red 70 Excellent OH Ho CH 0 I 0 CH Q Q N N N N 68 Brown 52Excellent OH HO R cl-l 0 CH 0 cll o CH O N NO 2 2 Q N -N N OH HO 3 Q N:NN Orange 65 Good )L l cH Table III-Continued ('oluur Ex, Ligand Productin 1 Fustncss [.ucqucr Yield to Light 70 Red 51 Good z Q CH3 3 HO o/Nl\OH CH CH3 0mg Q CH3 7| CH3 N N No Red 100 Good 2 N CH0 Nd N 2 h 3 0 3 OHH CH 2 CH 72 Q CH3 3 0 Red 100 Good N N- No 2 NN- 2 N N QI o CH HO CH an N 7 d 73 N N N -NO2 Brown 9 G00 Cu 0/ 0 CH3 EXAMPLE 74 60 Parts of theproduct of Example 21 were ball milled with 138 parts ofa solution of anunmodified bu tylated melamine/formaldehyde resin in n-butanol and 452parts of xylol. 350 parts of a solution of a hydroxy acrylic resin, a1:1 mixture of xylene and n-butanol, were added gradually and ballmilling continued. The resulting mixture had a pigment to binder ratioof 1:5; this was adjusted to 1:10 by the addition of more resin solutionand the paint was thinned to the required viscosity for spraying.Aluminium panels were sprayed and then stoved at 120C for minutes. Theresulting paint films had excellent fastness to light, heat and acids;for example, spotting the panels with 0.1 N hydrochloric acid left nodiscolouration after drying, and stoving the panels at 180C for 30minutes had practically no detectable effect on the colour. Theresulting coated panels were a very attractive transparent red colourand could be oversprayed with for example, a white paint of the sametype without the red colour bleeding into and thus spoiling the newwhite finish.

When the stainer (with a 1:5 pigment to binder ratio) whose preparationis described above was combined with a suitable paste of finely powderedaluminium to give a pigment to aluminium ratio of 75:25 and the mixturewas again thinned to a suitable viscosity for spraying, very atractivebronze yellow metallic coatings were obtained which also had excellentfastness properties.

' 1n the same way by replacing the product of Example 21 with theproducts of any of the Examples 22-73 there could be obtained paintfilms having varying shades of yellow to red. All were however,characterized by having the same excellent fastness properties.-

We claim: 1. An unsymmetrical conipound having either the formula:

wherein M is Cu, Ni or Zn, X and Y are the same or different, and eachis hydrogen or each represents a non water solubilising group, selectedfrom the group consisting of halogen, alkyl having from 1 to 4 carbonatoms, alkoxy having from 1 to 4 carbon atoms, nitro, or carboxy, and Zhas the same significance as X and Y, or two adjacent X groups or twoadjacent Y groups or two adjacent Z groups form a fused naphthalenering, and k, m and n are the same or different and each is an integerfrom 1 to 4 with the proviso that when Y, Z are the same, then thepositions of Y and Z in their respective benzene nuclei are differentrelative to the respective oxygen atoms attached to these nuclei; or theformula:

wherein M, X, Y, m and k have their previous significance, R and R arethe same or different and each is an alkyl having from 1 to 4 carbonatoms or an aryl selected from the group consisting of phenyl,a-naphthyl and Bmaphthyl, and R is hydrogen or an arylazo selected fromthe groups consisting of phenylazo, a-naphthylazo and B-naphthylazo.

2. A compound as claimed in claim 1, wherein M is a copper or nickel.

3. A compound as claimed in claim 1, wherein X, Y and Z are non watersolubilising groups selected from halogen, alkyl having from 1 to 4carbon atoms, alkoxy having from 1 to 4 carbon atoms, nitro, carboxy orform a naphthylene ring with the group to which they are attached.

4. A compound of formula ll according to claim 1 wherein R is hydrogen.

5. A compound according to claim 1 having the formula:

wherein X, is a halogen or alkyl having 1 to 4 carbon atoms, Y ishydrogen or carboxy] and Z is hydrogen, phenylazo or halogen.

6. A compound as claimed in claim 1 and having the formula:

wherein M is Cu, Ni or Zn, X and Y are the same or different, and eachis hydrogen or each represents a non water solubilising group selectedfrom the group consisting of halogen, alkyl of l to 4 carbon atoms,alkoxy of l to 4 carbon atoms, nitro, or carboxy and Z has the samesignificance as X and Y, or two adjacent X groups or two adjacent Ygroups or two adjacent Z groups form a fused naphthylene ring, and k, mand n are the same or different and each is an integer from 1 to 4 withthe proviso that when Y, Z are the same. then the positions of Y and Zin their respective benzene nuclei are different relative to therespective oxygen atoms attached to these nuclei; comprising reacting acompound having the formula:

(X) N CH p (D III with an o-hydroxy aldehyde having the formula:

CHO

to produce a compound having the formula:

HC=N =CH V and then metallising the compound V.

8. A process as claimed in claim 7, wherein the reaction betweencompounds I11 and IV is effected in solution or in a finely-dispersedsuspension with good agitation, using water as the reaction medium.

9. A process as claimed in claim 7, wherein the reaction between thecompounds 111 and IV is effected at a temperature between 50C. and thereflux temperature of the mixture.

10. A process as claimed in claim 7, wherein the metallisation ofcompound V is carried out in situ or the compound V is filtered off,washed and resuspended in the same or a different solvent prior tometallisation.

11. A process as claimed in claim 7, wherein an aqueous solution ofcopper acetate, cuprammonium sulphate or sodium cuprotartrate is usedfor metallisation.

12. A process as claimed in claim 7, wherein a solution of nickelacetate tetrahydrate in dimethyl formamide is used for metallisation.

wherein Y, Z, M, m and n are as defined in claim 1, to

'produce a compound of formula 1; or with a metal salt of acorresponding ,B-diketone, the salt having the formula:

c o mil-C g X 2 VII.

co I

1. AN UNSYMMETRICAL COMPOUND HAVING EITHER THE FORMULA:
 2. A compound asclaimed in claim 1, wherein M is a copper or nickel.
 3. A compound asclaimed in claim 1, wherein X, Y and Z are non water solubilising groupsselected from halogen, alkyl having from 1 to 4 carbon atoms, alkoxyhaving from 1 to 4 carbon atoms, nitro, carboxy or form a naphthylenering with the group to which they are attached.
 4. A compound of formulaII according to claim 1 wherein R111 is hydrogen.
 5. A compoundaccording to claim 1 having the formula:
 6. A compound as claimed inclaim 1 and having the formula:
 7. A process of producing a compound ofthe formula:
 8. A process as claimed in claim 7, wherein the reactionbetween compounds III and IV is effected in solution or in afinely-dispersed suspension with good agitation, using water as thereaction medium.
 9. A process as claimed in claim 7, wherein thereaction between the compounds III and IV is effected at a temperaturebetween 50*C. and the reflux temperature of the mixture.
 10. A processas claimed in claim 7, wherein the metallisation of compound V iscarried out in situ or the compound V is filtered off, washed andresuspended in the same or a different solvent prior to metallisation.11. A process as claimed in claim 7, wherein an aqueous solution ofcopper acetate, cuprammonium sulphate or sodium cuprotartrate is usedfor metallisation.
 12. A process as claimed in claim 7, wherein asolution of nickel acetate tetrahydrate in dimethyl formamide is usedfor metallisation.
 13. A process for the production of a compound offormula I or II comprising reacting a compound of formula III as definedin claim 7 with, respectively, a metal salt of an o-hydroxy aldehyde offormula IV as defined in claim 7, the salt having the formula: